Diaryl yellow pigment preparations

ABSTRACT

The invention relates to a diaryl yellow pigment preparation, including a) at least one diaryl yellow pigment. b) at least one natural resin on the basis of rosin or modified rosin, c) at least one compound of formula (1), and d) an aluminum, zinc, manganese or iron compound in an amount of from 0.1 to 8% by weight (calculated as a metal cation), based on component b). The inventive preparations are suitable for a variety of applications, among them the production of printing inks, especially offset printing inks.

[0001] The invention relates to diaryl yellow pigments prepared with aspecial combination of natural resin derivatives and having improvedperformance properties when used in offset printing inks.

[0002] Offset printing inks are subject to particular requirements asregards rheology, i.e., the viscosity and fluidity, and as regardscoloristics, such as color strength, for example. Offset printing inksought on the one hand to possess a high fluidity, in order to besuitable for use in high-speed rotary Offset machines. On the other handan increase in the viscosity at high shear rates, such as occur in theroll nips and in the plate cylinders of the printing machines,counteracts the misting of the printing ink.

[0003] In dependence on the nature of the pigment class a variety ofmethods of preparing the pigment particles have been proposed.

[0004] EP-A-0 313 360 discloses preparing azo pigments andphthalocyanine pigments with an equimolar amount, based on the pigment,of a pine resin and with an aluminum salt, in order to improvedispersing and raise color strength in printing inks.

[0005] In EP-A-0 671 443 the tendency of resinated pigments towardself-heating is lowered by addition of polyvalent metals to the aqueouspigment suspension.

[0006] JP-A-10 120930 proposes preparing disazo pigments with abieticacid and with a mixture of a Ca salt and an Al salt.

[0007] The stated methods of the prior art have deficiencies,particularly as regards diaryl yellow pigments, in color strength, inviscosity and/or in fluidity.

[0008] The object was therefore to prepare diaryl yellow pigments suchthat they have high fluidity, a high viscosity, and good coloristicproperties, such as high color strength, for example.

[0009] It has been found that a combination of diaryl yellow pigmentswith natural resin, certain abietic acid derivatives, and a definedamount of an Al, Zn, Mn or Fe compound surprisingly achieves the statedobject.

[0010] The present invention provides a diaryl yellow pigmentpreparation comprising

[0011] a) at least one diaryl yellow pigment,

[0012] b) at least one natural resin based on rosin or modified rosin,

[0013] c) at least one compound of the formula (1)

[0014]  in which the ring A is saturated, unsaturated or aromatic andthe ring B is saturated or unsaturated;

[0015] X for a group of the formulae —CH₂—CH₂—, —CH₂CH(CH₃)— or—CH(CH₃)CH₂—, or a combination thereof, when x>1;

[0016] x¹ and x² are a number from 0 to 16, the sum of x¹ and x² being anumber from 2 to 20;

[0017] D¹ and D² are identical or different and are a saturated orolefinic C₁-C₄-hydrocarbon radical;

[0018] A^(β) and A^(2⊕) are an ammonium ion of an amine of the formula

H₂N—(CR¹R²)_(y) ¹—(NR³—(CR¹R²)_(y) ²—)_(z)—NR⁴R⁵

[0019]  in which R¹ to R⁵ are identical or different and are hydrogen,methyl or ethyl, y¹ and y² are each a number from 1 to 4, and x is anumber from zero to 10; and

[0020] d) an aluminum, zinc, manganese or iron compound in an amount offrom 0.1 to 8% by weight (calculated as metal cation), based oncomponent b),

[0021]  and if desired

[0022] e) a polyesteramide and/or customary auxiliaries.

[0023] By diaryl yellow pigments a) are meant in general those of theformula (2)

[0024] in which Ar¹ and Ar² are identical or different and are anunsubstituted phenyl group or a phenyl group substituted by from one tothree substituents from the group consisting of halogen, such aschlorine, methyl, and methoxy.

[0025] Preferred diary yellow pigments for the purposes of the presentinvention are C.I. P. Yellow 12, 13, 14, 17, 126, 127, 174, 176, and188.

[0026] By a natural resin b) are meant, in general, natural resin acids,their hydrogenation products and disproportionation products, andDiels-Alder adducts of rosin and maleic anhydride, the stated resincompounds preferably being in the form of the commercially customarytypes of rosin or obtained therefrom. Natural resin acids are, forexample, abietic acid, dehydroabietic acid, dihydroabietic acid,tetrahydroabietic acid, levopimaric acid, dextropimaric acid, andisodextropimaric acid, and mixtures thereof.

[0027] Component c) is derived preferably from abietylamine, dehydro- ordihydroabietylamine. Furthermore, x¹ and x² are preferably a number from1 to 10, the sum of x¹ and x² being preferably from 4 to 16. D¹ and D²are preferably —CH₂—, CH₂CH₂—, —(CH₂)₄—, and —CH═CH—, especially—CH═CH—; and y¹ and y² are each preferably 2 or 3, and z is preferably anumber from 1 to 4.

[0028] Particular preference is given to the compound of the formula(1a)

[0029] in which X is as defined above,

[0030] x³ and x⁴ are each a number from 2 to 8 and the sum of x³ and x⁴is a number from 6 to 12, and

[0031] y³ is the number 2 or 3.

[0032] Compounds of the formula (1) are described in EP-B1-0 513 782 orcan be prepared analogously.

[0033] As component d) it is preferred to use salts of Al, Zn, Mn, andFe, e.g., the sulfates, carbonates, chlorides, nitrates, alkoxides, andcarboxylates, such as acetate or citrate, for example, or elsehydroxides of Al, Zn, Mn, and Fe. The stated compounds may contain usualamounts of water of crystallization.

[0034] As component e) it is possible to add further auxiliaries, suchas dispersants, e.g., polyesteramides, or anionic, cationic or nonionicsurfactants, such as alcohol alkoxylates, for example.

[0035] Preferred pigment preparations are composed essentially of

[0036] 50 to 90% by weight, in particular 60 to 80% by weight, ofcomponent a),

[0037] 5 to 45% by weight, in particular 10 to 38% by weight, ofcomponent b),

[0038] 0.2 to 5% by weight, in particular 0.5 to 2% by weight, ofcomponent c),

[0039] 0.05 to 2% by weight, in particular 0.3 to 1.5% by weight, ofcomponent d), calculated as metal cation, and

[0040] 0 to 5% by weight, in particular 1.8 to 3.6% by weight, ofcomponent e), based in each case on the total weight (100% by weight) ofthe pigment preparation.

[0041] The invention also provides a process for preparing the diarylyellow pigment preparation, which comprises coupling anacetoacetylanilide with a tetrazonium salt of 3,3′-dichlorobenzidine inthe presence of component c); combining the resulting pigment suspensionwith an aqueous-alkaline solution of component b) and heating it to atemperature between 65 and 150° C.; adding component d) in an amount offrom 0.1 to 8% by weight, based on component b), and subsequentlyprecipitating the diaryl yellow pigment preparation by acidification andisolating it.

[0042] The diazo component, 3,3′-dichlorobenzidine, can be diazotized bystandard methods.

[0043] The coupling component used is, for example, acetoacetic anilide,acetoacetic o-toluidide, acetoacetic m-toluidide, acetoaceticm-xylidide, acetoacetic anisidide, acetoacetic2,5-dimethoxy-4-chloroanilide or a mixture thereof, appropriately inaqueous or aqueous-organic suspension.

[0044] In one particularly preferred embodiment the suspension of thecoupling component is admixed with an emulsion of a polyesteramide in,for example, an amount of from 1.8 to 3.6% by weight, based on the totalmass of the pigment preparation.

[0045] The azo coupling takes the place in the presence of one or morecompounds of the formula (1) which can be added in the form of anaqueous solution either to the coupling suspension or to the tetrazoniumsalt of 3,3′-dichlorobenzidine, or to both, or the stated reactants canbe combined. The azo coupling takes place preferably in aqueous oraqueous-organic medium, with preference at a pH between 3 and 7, inparticular between 4 and 6, and at a temperature between 15 and 30° C.,in particular between 20 and 25° C.

[0046] After the coupling the pigment suspension is admixed with anaqueous-alkaline solution, e.g., in dilute sodium hydroxide or potassiumhydroxide solution, of a natural resin b), the amount of resin, based onpigment, being from 10 to 80% by weight, preferably from 20 to 70% byweight. Subsequently the mixture is heated for preferably at least 15minutes, normally from 30 minutes to 10 hours, at a temperature of from65 to 150° C., preferably from 80 to 120° C., more preferably from 85 to100° C.

[0047] The metal compound (component d) is then added in solid,dissolved or suspended form at a temperature between 40 and 100° C.,preferably in an amount of from 0.1 to 8% by weight, more preferablyfrom 1 to 4% by weight (calculated as metal cation), based on componentb). The pH of the mixture ought to be between 7.1 and 14. Subsequently,using for example hydrochloric, sulfuric or acetic acid, a pH ofpreferably from 2 to 6, more preferably from 3 to 5, is set, and thediaryl yellow pigment preparation of the invention precipitates out. Thesuspension is filtered and the solid product is washed free of salt,dried, and, where appropriate, ground.

[0048] The pigment preparations of the invention can be dispersed easilyin varnishes customary for offset printing inks, e.g., for sheet fedoffset, roller offset or newspaper printing, and give printing inks ofhigh color strength and particularly good rheological properties,specifically improved fluidity coupled with high viscosities with highshear rates.

[0049] The invention also provides for the use of the above-describeddiaryl yellow pigment preparation for producing printing inks,especially offset printing inks.

[0050] The pigment preparations of the invention are further suitable ascolorants in electrophotographic toners and developers, such asone-component or two-component powder toners (also called one-componentor two-component developers), magnetic toners, liquid toners,polymerization toners, and further, specialty toners (i.e. Schein,“Electrophotography and Development Physics”; Springer Series inElectrophysics 14, Springer Verlag, 2nd edition, 1992). Additionally thepigment preparations of the invention are suitable as colorants ininkjet inks on an aqueous and a nonaqueous basis, and also in those inkswhich operate in accordance with the hotmelt process or are based onmicroemulsions.

[0051] In the examples below the color strength was determinedcalorimetrically from test-rig sample prints on art printing paper ApcoII/II (from Scheuffelen, Oberlenningen) with an ink application of 1.5g/m².

[0052] The viscosities were determined on a Laray viscometer, theviscosity being read off at 12 Laray seconds.

[0053] For the determination of the fluidity, 1 g of the offset ink wasapplied to a sloping plane (45° angle) and a measurement was made of theflow path after a flow time of 3 seconds, in mm. The higher the result,the better the fluidity.

[0054] Parts denote parts by weight. Percentages denote percent byweight.

EXAMPLE 1

[0055] A coupling component suspension having a pH of 5.6, prepared from11.6 parts (30 mol %) of acetoacetic o-toluidide and 28.8 parts (70 mol%) of acetoacetic m-xylidide with 27.2 parts of 33% strength sodiumhydroxide solution in 500 parts of water and subsequent precipitationwith 80% strength acetic acid is admixed with 0.7 part of the compoundof the formula (1b)

[0056] with x¹+x²=4; y¹+y²=6.

[0057] Subsequently the suspension is coupled in one hour at a pH rangebetween 5.7 and 5.3 and at a temperature of from 20 to 25° C. with anapproximately 10% strength aqueous 3,3′-dichlorobenzidine tetraazosolution (prepared by bisdiazotizing 25.3 parts of3,3′-dichlorobenzidine in dilute HCl and sodium nitrite).

[0058] Sodium hydroxide solution is used to adjust the pH of the pigmentsuspension to 7.5, after which it is admixed with a resin solutioncomposed of 87.5 parts of water, 19 parts of disproportionated rosin and11.2 parts of 33% strength NaOH. The temperature of the suspension israised to 95° C. and held for 3 hours. At 65° C. (cooling with ice), thepH is deacidified to about 8 by addition of 8 parts of Al₂(SO₄)₃.18H₂O.After 30 minutes the suspension is adjusted to a pH of 5 usinghydrochloric acid and is filtered and the solid product is washed freeof salt, dried at 63° C. and ground on a pinned disk mill.

[0059] This gives 86.1 g of a diaryl yellow pigment preparationcontaining P.Y. 174.

COMPARATIVE EXAMPLE 1a Against EP-B-0 513 782

[0060] The procedure of example 1 is repeated but with the differencethat no Al sulfate is added.

COMPARATIVE EXAMPLE 1b Against EP-A-0 671 443

[0061] The procedure of example 1 is repeated but with the differencethat no compound of the formula (1b) is added.

COMPARATIVE EXAMPLE 1c Against EP-A-0 313 360

[0062] The procedure of example 1 is repeated but with the differencethat no compound of the formula (1b) is added and that 97.2% by weightof disproportionated rosin, based on pigment, is added.

EXAMPLE 2

[0063] A coupling component suspension having a pH of 5.6, prepared from3.9 parts of acetoacetic 2,5-dimethoxy-4-chloroanilide and 38.9 parts ofacetoacetic m-xylidide with 36 parts of 33% strength sodium hydroxidesolution in 500 parts of water and subsequent precipitation with 9.6parts of 80% strength acetic acid and 22.3 parts of 31% strengthhydrochloric acid is admixed with 0.86 part of the compound of theformula (1b). Subsequently the suspension is coupled in one hour at a pHrange between 5.6 and 4.5 and at a temperature of from 20 to 25° C. withan approximately 10% strength aqueous 3,3′-dichlorobenzidine tetraazosolution (prepared by bisdiazotizing 25.3 parts of DCB in dilute HCl andsodium nitrite).

[0064] Sodium hydroxide solution is used to adjust the pH of the pigmentsuspension to 7.5, after which it is admixed with a resin solutioncomposed of 150 parts of water, 37.5 parts of disproportionated rosinand 22.4 parts of 33% strength NaOH. The temperature of the suspensionis raised to 95° C. and held for 3 hours. At 65° C. (cooling with ice),the pH is deacidified to about 8 by addition of 15 parts ofAl₂(SO₄)₃.18H₂O. After 30 minutes the suspension is adjusted to a pH of5 using hydrochloric acid and is filtered and the solid product iswashed free of salt, dried at 60° C. and ground on a pinned disk mill.

[0065] This gives 107 g of a diaryl yellow pigment preparationcontaining P.Y. 176.

COMPARATIVE EXAMPLE 2a Against EP-B-0 513 782

[0066] The procedure of example 2 is repeated but with the differencethat no Al sulfate is added.

EXAMPLE 3

[0067] A coupling component suspension having a pH of 5.6, prepared from7.2 parts of acetoacetic anilide and 33.1 parts of acetoaceticm-xylidide with 27.2 parts of 33% strength sodium hydroxide solution in500 parts of water and subsequent precipitation with 80% strength aceticacid is admixed with 0.7 part of the compound of the formula (1b).Subsequently the suspension is coupled in one hour at a pH of 5.5 (pH isheld constant by simultaneous introduction of NaOH solution) at atemperature of from 20 to 25° C. with an approximately 10% strengthaqueous 3,3′-dichlorobenzidine tetraazo solution (prepared bybisdiazotizing 25.3 parts of DCB in dilute HCl and sodium nitrite).

[0068] Sodium hydroxide solution is used to adjust the pH of the pigmentsuspension to 11, after which it is admixed with a resin solutioncomposed of 188 parts of water, 32.5 parts of disproportionated rosinand 20.0 parts of 33% strength NaOH. The temperature of the suspensionis raised to 95° C. and held for 0.5 h. At 65° C. (cooling with ice),the pH is deacidified to about 9 by addition of 13 parts ofAl₂(SO₄)₃.18H₂O. After 30 minutes the suspension is adjusted to a pH of5 using hydrochloric acid and is filtered and the solid product iswashed free of salt, dried at 60° C. and ground on a pinned disk mill.

[0069] This gives 99 g of a diaryl yellow pigment preparation containingP.Y. 188.

COMPARATIVE EXAMPLE 3a Against EP-B-0 513 782

[0070] The procedure of example 3 is repeated but with the differencethat no Al sulfate is added.

EXAMPLE 4

[0071] A coupling component suspension having a pH of 5.6, prepared from8.55 parts of acetoacetic o-anisidide and 32.8 parts of acetoaceticm-xylidide with 40.8 parts of 33% strength sodium hydroxide solution in292 parts of water and subsequent precipitation with 10.8 parts of 80%strength acetic acid and about 25.5 parts of 31% strength hydrochloricacid is admixed with 0.65 part of the compound of the formula (1b).Subsequently the suspension is coupled in one hour at a pH range between5.6 and 4.5 and at a temperature of from 20 to 25° C. with anapproximately 10% strength aqueous 3,3′-dichlorobenzidine tetraazosolution (prepared by bisdiazotizing 25.3 parts of DCB in dilute HCl andsodium nitrite).

[0072] Sodium hydroxide solution is used to adjust the pH of the pigmentsuspension to approximately 11, after which it is admixed with a resinsolution composed of 75 parts of water, 18.8 parts of rosin and 9.5parts of 33% strength NaOH. The temperature of the suspension is raisedto 95° C. and held for 2 hours. At 65° C. (cooling with ice), and the pHis deacidified to about 8 by addition of 10 parts of Al₂(SO₄)₃.18H₂O.After 30 minutes the suspension is adjusted to a pH of 5 usinghydrochloric acid and is filtered and the solid product is washed freeof salt, dried at 63° C. and ground on a pinned disk mill.

[0073] This gives 84.2 g of a diaryl yellow pigment preparationcontaining P.Y. 127.

COMPARATIVE EXAMPLE 4a Against EP-B-0 513 782

[0074] The procedure of example 4 is repeated but with the differencethat no Al sulfate is added.

EXAMPLE 5

[0075] The procedure of example 1 is repeated but with the differencethat following the addition of the compound of the formula (1b) anemulsion of 2.75 parts of polyesteramide in water is added as well tothe arylide solution.

[0076] Instead of the resin solution of example 1 a resin solution isused which is composed of 150 parts of water, 30 parts ofdisproportionated rosin and 19.0 parts of 33% strength NaOH. The amountof Al₂(SO₄)₃.18H₂O is 12 parts.

[0077] This gives 101 g of a diaryl yellow pigment preparationcontaining P.Y. 174.

COMPARATIVE EXAMPLE 5a Against EP-B-0 513 782

[0078] The procedure of example 5 is repeated but with the differencethat no Al sulfate is added.

EXAMPLE 6

[0079] The procedure of example 2 is repeated but with the differencethat following the addition of the compound of the formula (1b) anemulsion of 3 parts of polyesteramide in water is added as well to thearylide solution.

[0080] The amount of Al₂(SO₄)₃.18H₂O is 16 parts.

[0081] This gives 110 g of a diaryl yellow pigment preparationcontaining P.Y. 176.

COMPARATIVE EXAMPLE 6a Against EP-B-0 513 782

[0082] The procedure of example 6 is repeated but with the differencethat no Al sulfate is added.

EXAMPLE 7

[0083] A coupling component suspension having a pH of 5.6, prepared from11.6 parts (30 mol %) of acetoacetic o-toluidide and 28.8 parts (70 mol%) of acetoacetic m-xylidide with 27.2 parts of 33% strength sodiumhydroxide solution in 500 parts of water and subsequent precipitationwith 80% strength acetic acid is admixed with 0.7 part of the compoundof the formula (1b). Subsequently the suspension is coupled in one hourat a pH range between 5.7 and 5.3 and at a temperature of from 20 to 25°C. with an approximately 10% strength aqueous 3,3′-dichlorobenzidinetetraazo solution (prepared by bisdiazotizing 25.3 parts of DCB indilute HCl and sodium nitrite).

[0084] Sodium hydroxide solution is used to adjust the pH of the pigmentsuspension to approximately 7.5, after which it is admixed with a resinsolution composed of 150 parts of water, 30 parts of disproportionatedrosin and 14 parts of 33% strength NaOH. The temperature of thesuspension is raised to 95° C. and held for 3 hours. At 65° C. (coolingwith ice), 20.8 parts of ZnCl₂ are added. The pH is adjusted to 9 usingHCl. After 30 minutes the suspension is adjusted to a pH of 5 usinghydrochloric acid and is filtered and the solid product is washed freeof salt, dried at 63° C. and ground on a pinned disk mill.

[0085] This gives 96.4 g of a diaryl yellow pigment preparationcontaining P.Y. 174.

EXAMPLE 8

[0086] The procedure of example 7 is repeated but with the differencethat instead of the addition of the Zn salt 13 parts of FeCl₂ are added.

[0087] This gives 102.7 g of a diaryl yellow pigment preparationcontaining P.Y. 174.

EXAMPLE 9

[0088] The procedure of example 7 is repeated but with the differencethat instead of the addition of the Zn salt 20 parts of MnCl₂.4H₂O areadded.

[0089] This gives 98.7 g of a diaryl yellow pigment preparationcontaining P.Y. 174.

USE EXAMPLES

[0090] The pigment preparations of the examples above are used toproduce offset inks, by stirring the ground pigment preparation into theoffset varnish below and dispersing the composition on a triple-rollmill. The printing inks thus produced are tested after storage for 24hours.

[0091] The corresponding printing inks have the following compositions:

[0092] 12.0 parts pigment preparation

[0093] 38.0 parts ®Albertol VKP 1385 (from Solutia, Germany)

[0094] 4.5 parts ®Vialkyd AL 766 (from Solutia, Germany)

[0095] 42.5 parts printing ink oil PKW F 6/9 (from Haltermann, Hamburg)

[0096] 2.8 parts ®Printael (SUN Chemical-Hartmann, Frankfurt)

[0097] 0.2 Dart siccative

[0098] 100.0 parts.

[0099] The results are shown in the table below. TABLE Pigmentpreparation of Fluidity in Laray viscosity Color strength* example mm inPa · s in % 1 50 29 105 Comparative example 1a 17 19 109 Comparativeexample 1b 12 26 84 Comparative example 1c 0 31 55 2 25 30 104Comparative example 2a 13 13 108 3 87 18 88 Comparative example 3a 60 1288 4 54 28 102 Comparative example 4a 27 16 104 5 83 24 100 Comparativeexample 5a 43 12 105 6 86 24 99 Comparative example 6a 56 12 104 7 40 20104 8 58 23 109 9 114 36 111

[0100] It is evident that only the examples in accordance with theinvention possess both a high fluidity and a high Laray viscosity. Thepigment preparations of comparative example 1b and 1c have deficienciesin color strength.

1. A diaryl yellow pigment preparation comprising a) at least one diarylyellow pigment, b) at least one natural resin based on rosin or modifiedrosin, c) at least one compound of the formula (1)

 in which the ring A is saturated, unsaturated or aromatic and the ringB is saturated or unsaturated; X is selected from the group consistingof —CH₂—CH₂—, —CH₂CH(CH₃)— or —CH(CH₃)CH₂—, and a combination thereof;x¹ and x² are a number from 0 to 16, the sum of x¹ and x² being a numberfrom 2 to 20; D¹ and D² are identical or different and are a saturatedor olefinic C₁-C₄-hydrocarbon radical; A^(⊕) and A^(2β) are an ammoniumion of an amine of the formula H₂N—(CR¹R²)_(y) ¹—(NR³—(CR¹R²)_(y)²—)_(z)—NR⁴R⁵  in which R¹ to R⁵ are identical or different and arehydrogen, methyl or ethyl, y¹ and y² are each a number from 1 to 4, andz is a number from zero to 10; and d) an aluminum, zinc, manganese oriron compound in an amount of from 0.1 to 8% by weight (calculated asmetal cation), based on component b).
 2. A diaryl yellow pigmentpreparation as claimed in claim 1, wherein the diaryl yellow pigment a)is a compound of the formula (2)

in which Ar¹ and Ar² are identical or different and are an unsubstitutedphenyl group or a phenyl group substituted by from one to threesubstituents selected from the group consisting of halogen, methyl, andmethoxy.
 3. A diaryl yellow pigment preparation as claimed in claim 1,wherein the diaryl yellow pigment is C.I. Pigment Yellow 12, 13, 14, 17,126, 127, 174, 176, 188 or a mixture thereof.
 4. A diaryl yellow pigmentpreparation as claimed in claim 1, wherein the natural resin b) isabietic acid, dehydroabietic acid, dihydroabietic acid,tetrahydroabietic acid, levopimaric acid, dextropimaric acid,isodextropimaric acid, or a mixture thereof.
 5. A diaryl yellow pigmentpreparation as claimed in claim 1, wherein in the compound of theformula (1) x¹ and x² are a number from 1 to 10, the sum of x¹ and x²being from 4 to 16; D¹ and D² are —CH₂—, CH₂CH₂—, —(CH₂)₄— or —CH═CH—;y¹ and y² are each the number 2 or 3; and z is a number from 1 to
 4. 6.A diaryl yellow pigment preparation as claimed in claim 1, wherein c) isa compound of the formula (1a)

in which X is as defined in claim 1; x³ and x⁴ are each a number from 2to 8 and the sum of x³ and x⁴ is a number from 6 to 12, and y³ is thenumber 2 or
 3. 7. A diaryl yellow pigment preparation as claimed inclaim 1, wherein component d) is a sulfate, carbonate, chloride,nitrate, alkoxide, carboxylate, acetate, citrate or hydroxide of metalsAl, Zn, Mn or Fe.
 8. A diaryl yellow pigment preparation as claimed inclaim 1, consisting essentially of 50 to 90% by weight of component a),5 to 45% by weight of component b), 0.2 to 5% by weight of component c),and 0.05 to 2% by weight of component d), calculated as metal cation,based in each case on the total weight (100% by weight) of the pigmentpreparation.
 9. A process for preparing a diaryl yellow pigmentpreparation as claimed in claim 1, comprising the steps of coupling anacetoacetylanilide with a tetrazonium salt of 3,3′-dichlorobenzidine inthe presence of component c); combining the resulting pigment suspensionwith an aqueous-alkaline solution of component b) and heating to atemperature between 65 and 150° C.; adding component d) in an amount offrom 0.1 to 8% by weight, based on component b), and subsequentlyprecipitating the diaryl yellow pigment preparation by acidification andisolating itthe diaryl yellow pigment preparation.
 10. A printing inkcomprising the diaryl yellow pigment preparation as claimed in claim 1.11. A diaryl yellow pigment preparation as claimed in claim 1,comprising: 50 to 90% by weight of component a), 5 to 45% by weight ofcomponent b), 0.2 to 5% by weight of component c), and 0.05 to 2% byweight of component d), calculated as metal cation, based in each caseon the total weight (100% by weight) of the pigment preparation.
 12. Atoner colorant comprising the diaryl yellow pigment preparation asclaimed in claim
 1. 13. The toner colorant as claimed in claim 12,wherein the toner is selected from the group consisting ofelectrophotographic toners and developers, magnetic toners, liquidtoners, polymerization toners and specialty toners.
 14. An inkjet inkcolorant comprising the diaryl yellow pigment preparation as claimed inclaim
 1. 15. A diaryl yellow pigment preparation as claimed in claim 1,further comprising a polyesteramide.